Recently the change from expensive electrotinplates to cheaper tin free steel (TFS-CT) having double layers consisting of a lower layer of metallic chromium and an upper layer of hydrated chromium oxide as well as a decrease in the weight of the tin coating in electrotinplates has rapidly taken place in the field of food cans.
This is because the tin used for the production of tinplate is very expensive and there is concern over the exhaustion of tin resources in the world.
An ordinary metal can consists of two can ends and a single can body, except for drawn cans. In the case of tinplate, the seaming of the can body is generally carried out by soldering. In this soldering process, however, it is impossible to decrease the weight of the tin coating on the tinplate to under 2.8 g/m.sup.2, because it is difficult to stabilize the soldering process when the weight of the tin coating is under 2.8 g/m.sup.2. From the regulation of lead content in the solder used for the seaming of the tinplate can body in the field of food cans, the seaming of the tinplate can body is widely carried out by electric welding. A lap seam welding, for instance, the Soudronic process, has been recently used for the seaming of the tinplate can body.
In this process, it is desirable to decrease the tin coating weight in the tinplate, but the weldability of tinplate becomes poor with a decrease of the tin coating weight.
On the other hand, the seaming of a TFS-CT can body is generally carried out with nylon adhesives using Toyo Seam (trademark) and Mira Seam (trademark) methods. Another method of seaming a TFS-CT can body by electric welding is also well known. In the case of the seaming of a TFS-CT can body by electric welding, however, the metallic chromium layer and the hydrated chromium oxide layer must be mechanically removed from the TFS-CT surface in order to easily weld the TFS-CT can body at high speed. Therefore, the corrosion resistance in the welded part of the TFS-CT can body becomes remarkably poor, even if this welded part is coated with lacquer after welding.
From the background described above, the development of a can material which is cheaper than tinplate, is easily welded at high speed without the removal of the plated layer, has been required in the field of food cans.
Recently, various surface treated steel sheets have been proposed as a can material which can be easily welded at high speed without the removal of the plated layer. For instance, the following surface treated steel sheets have been proposed:
(a) Lightly tin coated steel sheet (LTS) with below about 1.0 g/m.sup.2 of tin which is reflowed or unreflowed after tin plating (Japanese Patent Publication Nos. Sho 56-3440, Sho 56-54070, Sho 57-55800, and Laid-Open Japanese Patent Application Nos. Sho 56-75589, Sho 56-130487, Sho 56-156788, Sho 57-101694, Sho 57-185997, Sho 57-192294, Sho 57-192295 and Sho 55-69297). PA1 (b) Nickel preplated LTS with below about 1.0 g/m.sup.2 of tin (Laid-Open Japanese Application Nos. Sho 57-23091, Sho 57-67196, Sho 57-110685, Sho 57-177991, Sho 57-200592 and Sho 57-203797). PA1 (c) Nickel plated steel sheet with chromate film or phosphate film (Laid-open Japanese Patent Application Nos. Sho 56-116885, Sho 56-169788, Sho 57-2892, Sho 57-2895, Sho 57-2896, Sho 57-2897, Sho 57-35697 and Sho 57-35698). PA1 (d) TFS-CT having double layers consisting of a lower layer of metallic chromium and an upper layer of hydrated chromium oxide which is obtained by some special methods such as cold rolling after TFS treatment (Laid-open Japanese Patent application No. Sho 55-48406), porous chromium plating (Laid-open Japanese Patent Application No. Sho 55-31124) and a cathodic treatment of a steel sheet in chromic acid electrolyte with fluoride but without anions such as sulfate, nitrate and chloride ions (Laid-open Japanese Patent Application No. Sho 55-18542). PA1 Concentration of chromic acid: 30-300 g/l, more preferably 80-300 g/l PA1 Concentration of additives: 1.0-5.0 weight %, more preferably 1.0-3.0 weight % of the concentration of chromic acid PA1 Additives: at least one compound selected from the group consisting of fluorine compounds and sulfur compounds PA1 Temperature of the electrolyte: 30.degree.-60.degree. C. PA1 Cathodic current density: 10-100 A/dm.sup.2 PA1 (A) An immersion of the chromium plated steel base before drying into a high concentration of an alkaline such as an alkali metal hydroxide and an alkali metal carbonate at high temperature of 70.degree. to 90.degree. C. It is difficult to industrialize this method because the alkaline solution may be mixed into the following nickel-zinc alloy plating electrolyte. PA1 (B) An immersion of the chromium plated steel base before drying into an acid solution such as sulfuric acid and hydrochloric acid. The method is not suitable in the present invention, because the hydrated chromium oxide formed during chromium plating is not sufficiently dissolved by immersion into an acid solution for a short time. PA1 (C) A mechanical removal of hydrated chromium oxide by a brushing roll or wiper in an alkaline solution or an acid solution before drying of the chromium plated steel base. The hydrated chromium oxide formed on the deposited metallic chromium layer is not uniformly removed by this method. PA1 Electrolyte: An acid solution containing at least one acid selected from the group consisting of sulfuric acid, hydrochloric acid, hydro-fluoric acid, fluoboric acid and fluosilicic acid having a pH of 0.5 to 2.0 PA1 Temperature of the electrolyte: 30.degree.-70.degree. C. PA1 Cathodic current density: 2-50 A/dm.sup.2 PA1 Treating time: 0.5-5.0 seconds PA1 Concentration of nickel ion: 15-80 g/l PA1 Concentration of zinc ion: 0.5-16 g/l PA1 Concentration ratio of zinc ion to nickel ion: 0.03-0.2 PA1 pH of the electrolyte: 0.5-2.0 PA1 Temperature of the electrolyte: 30.degree.-70.degree. C., more preferably 30.degree.-50.degree. C. PA1 Cathodic current density: 2-50 A/dm.sup.2, more preferably 2-30 A/dm.sup.2 PA1 Concentration of nickel ion: 15-80 g/l PA1 Concentration of zinc ion: 0.5-16 g/l PA1 Concentration ratio of zinc ion to nickel ion: 0.03-0.2 PA1 pH of the electrolyte: 0.5-5.5 PA1 Temperature of the electrolyte: 30.degree.-70.degree. C. PA1 Cathodic current density: 2-50 A/dm.sup.2 PA1 Concentration of hexavalent chromium ion: 5-30 g/l PA1 Temperature of the electrolyte: 30.degree.-70.degree. C. PA1 Cathodic current density: 1-20 A/dm.sup.2 PA1 Quantity of electricity: 1-40 coulombs/dm.sup.2 PA1 Concentration chromic acid: 10-50 g/l PA1 Weight percent of additives to chromic acid: 0.2-1.0 PA1 Additives: Sulfur compound and/or fluorine compound PA1 Temperature of the electrolyte: 30.degree.-60.degree. C. PA1 Cathodic current density: 1-10 A/dm.sup.2
However, LTS and nickel preplated LTS above identified as (a) and (b) are slightly more expensive than TFS-CT. Furthermore, these have not only narrower available current range for sound welding than that in tinplate, but also poor lacquer adhesion compared with that in TFS-CT, although these can be welded without the removal of the plated layer. The reason why the available current range for sound welding in LTS and nickel preplated LTS is narrower than in tinplate is considered to be that the amount of free tin in these is smaller than that in tinplate and also further decreases because of changes of free tin to iron-tin alloy by heating for lacquer curing. Nickel plated steel sheet with chromate film or phosphate film identified above as (c) also has narrower available current range for sound welding than that in LTS or nickel preplated LTS. Furthermore, the corrosion resistance of nickel plated steel sheet is poorer than that in TFS-CT, although the lacquer adhesion of nickel plated steel sheet is good.
Particularly, pitting corrosion in the defective part of the lacquered nickel plated steel sheet may occur easily from acidic foods such as tomato juice because the electrochemical potential of nickel is more noble than that of steel base and metallic chromium.
It is considered that the welding of TFS-CT identified above as (d) without the removal of TFS-CT film at high speed is very difficult because the oxide films having high electric resistance are formed by the oxidation of metallic chromium and exposed steel base and by the dehydration of hydrated chromium oxide during heating for curing the lacquer coating on the TFS-CT can body, although TFS-CT identified above as (d) may be welded when it is not heated before welding.
As described above, various surface treated steel sheets proposed in (a), (b), (c) and (d) have various problems in the production cost and the characteristics as a can material which can be easily welded without the removal of the plated layer at high speed.
Accordingly, it is the first objective of the present invention to provide a tin free steel sheet having an excellent weldability, that is, easily being welded without the removal of the plated layer at high speed, and having excellent corrosion resistance after lacquering such as that in TFS-CT.
It is the second objective of the present invention to provide a method for the continuous production of a tin free steel having an excellent weldability.